Crystallization of Supramolecular Materials: Perhydrotriphenylene (PHTP) Inclusion Compounds with Nonlinear Optical Properties

Abstract

A prerequisite for the design and synthesis of materials with nonlinear optical (NLO) properties is a molecular building block that can be incorporated into a solid in an appropriately functionalized and oriented manner. To obtain new, single-crystal materials that exhibit electrooptical (EO) effects more pronounced than those of the currently known organic NLO crystals,[' -41 stable molecules showing hyperpolarizabilities B, of up to 10000 x m 4 V 1 and. having dipole moments that can be aligned in a parallel manner within the solid are required. While a large number of target compounds can be envisioned based on these known criteria,I3. ' 1 the probability is low that during the crystallization of pure NLO compounds a crystal structure with a parallel arrangement of the b, axes is realized (about 25% for an acentric space group, less than 5 % for a nearly parallel Hence, the question of alternatives for the formation of crystalline and structurally optimized EO materials arises. In this study it is shown that perhydrophenylene (PHTP)I6] forms inclusion compounds with electronically optimized NLO species, in which the guest molecules can attain a parallel arrangement; materials with polar properties on a macroscopic level are formed about 90% of the time.

Polarity of Organic Supramolecular Materials: A Tunable Crystal Property

“…Finally, we will discuss an application where spontaneous polarity formation is possible, although some lateral interactions between polar chains of guest molecules may not promote a polar state. Practical examples comprise inclusion compounds of perhydrotriphenylene (PHTP) (15,16) forming inclusions with a large number of nonlinear optical (NLO) A} }D type molecules (17,18). For these materials the success rate of obtaining a polar crystal structure is over 90% (5).…”

Helical Coordination Polymers with Large Chiral Cavities

“…Second, replacement of a less critical CÀH moiety affords the same architecture as 1 a ± f. Specifically, 3 exhibits CÀH´´´p interactions and crystallizes with an almost identical structure, including cavities, to that of 1 a ± f (space group I4 1 22, a 14.8633(10), c 27.494(3) , V 6074.0 (8) 3 ). There are several observations and conclusions that we consider of particular relevance concerning the results reported herein: * It is becoming abundantly clear that chiral crystalline architectures and cavities or channels [19,20] can be achieved by using the most simple of achiral molecular components. Furthermore, the nature of the cavities means that achiral guests are induced to form chiral adducts.…”

Dynamics of the Triplet State of a Dithiophene in Different Solid Matrixes Studied by Transient and Pulse EPR Techniques

“…[2][3][4][5][6][7][8][9][10][11] When confined, such molecules are described as producing materials substantially different from those in the bulk phases. [12][13][14][15][16][17][18][19][20] The supramolecular organization of the molecules follows novel assembly principles and topological constrains resulting in anisotropic alignments and different conformational and motional behaviors. This confinement produces a conformational constraint strongly analogous to natural host-guest systems formed by light acceptors and proteins in biological systems.…”